Esters of phenyl ethers

ABSTRACT

ESTERS OF PHENYL ETHERS AND PHENYL THIOETHERS USEFUL FOR THE CONTROL OF INSECTS.

United States Patent Office 3,816,514 Patented June 11, 1974 3,816,514 ESTERS F PHENYL ETHERS John B. Siddall, Palo Alto, Calif., assignor to Zoecon Corporation, Palo Alto, Calif.

No Drawing. Original application Dec. 31, 1970, Ser. No. 103,278, now Patent No. 3,709,915. Divided and this application Mar. 6, 1972, Ser. No. 232,307

Int. Cl. C07c 69/14, 69/24, 69/ 62 U.S. Cl. 260-488 20 Claims ABSTRACT OF THE DISCLOSURE Esters of phenyl ethers and phenyl thioethers useful for the control of insects.

This is a division of application Ser. No. 103,278, filed Dec. 31, 1970 now U.S. Pat. 3,709,915.

This invention relates to novel compounds and the synthesis thereof useful for the control of insects. More particularly, the present invention relates to novel compounds of the following formulas I, H, and III, the synthesis thereof, and the control of insects.

wherein, m is the positive integer one or two; n is the positive integer two or three; each of Z and Z is hydrogen or taken together a carbon-carbon bond; each of R R R and R is lower alkyl; W is oxygen atom or sulfur atom; R is the residue of a carboxylic acid; R is one of the groups in which v is zero or the positive integer one; R is hydrogen, lower alkyl, cycloalkyl, aralkyl or lower alkoxy; X is halo, Y is lower alkyl, lower alkenyl, lower alkoxy, nitro, cyano, halomethyl, dihalomethyl, trihalomethyl, lower alkylthio, lower alkylsulfinyl or lower alkylsulfonyl; p is zero or a positive integer of one to five; and q is zero or a positive integer of one to three, the sum of p and q being from one to five.

The term halo, as used herein, refers to bromo, chloro, fluoro or iodo. The term lower alkyl, as used herein, refers to an alkyl group, straight or branched, having a chain length of one to six carbon atoms. The term cycloalkyl, as used herein, refers to a cycloalkyl of three to eight carbon atoms. The term aralkyl, as used herein, refers to aralkyl of seven to twelve carbon atoms, such as benzyl, phenethyl, methylbenzyl or naphthylmethyl. The term lower alkoxy, as used herein, refers to lower alkoxy of one to six carbons, such as methoxy, ethoxy and propoxy.

The novel compounds of formulas -I, II and :III are useful for the control of insects. The utility of these compounds as insect control agents is believed to be attributable to their juvenile hormone activity. They are preferably applied to the immature insect, namely-during the embryo, larvae or pupae stage in view of their ability to inhibit metamorphosis and otherwise cause abnormal development. These compounds are effective control agents for Hemipteran, such as Lygaeidae, Miridae and Pyrrhocoridae; Coleopteran, such as Tenebrionidae; Lepidopteran, such as Pyrali-dae, Noctiidae and Gelechiidae; Dipteran, such as mosquitoes; Orthoptera, such as roaches; and Homoptera, such as aphids. The compounds can be applied at low dosage levels of the order of 0.001 ,ug. to 25 ,ug. per insect. Suitable carrier substances include liquid or solid carriers, such as water, mineral or vegetable oils, talc, silica and natural or synthetic resin. The control of insects in accordance with the present invention is accomplished by spraying, dusting or exposing the insects to the vapor of the novel compounds. Generally, a concentration of less than 50% of the active compound is employed. The formulation can include insect attractants, emulsifying agents and wetting agents to assist in the application and efiiciency of the active ingredient.

The compounds of formulas I, II, and III include lower alkyl and lower alkoxy substituted phenyl, i.e. wherein Y is lower alkyl or lower alkoxy, which are exemplified by 4-ethylphenyl,

3-ethylphenyl,

2-ethylphenyl, 3,5-dimethylphenyl, 3,4-dimethylphenyl, 2,6-dimethylphenyl,

2,5 -dimethylphenyl, 2,4-dimethylphenyl, 2,3-dimethylphenyl, 2,6-dimethylphenyl diisopropylphenyl, 3,5 -di-t-butylphenyl, 2,6-di-sec-butylphenyl, 2,5-di-t-butylphenyl, 2,4-di-t-butylphenyl, 2,6-di-t-butyl-4-methylphenyl, 4-t-butylphenyl, 3-t-butylphenyl, 4-sec-butylphenyl, 2-t-butylphenyl, Z-sec-butylphenyl, 4-t-butyl-2-methylphenyl, 2-t-butyl-6-methylphenyl, Z-t-butyl-S-methylphenyl, 2-t-butyl-4-methylphenyl, 4-t-amylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 2-n-propylphenyl, 4-n-propylphenyl,

2,3,5 ,6-tetramethylphenyl, 2,4,6-tri-t-butylphenyl, 2,3,5-trimcthylphenyl, 2,3,6-trimethylphenyl, 2,4,6-trimethylphenyl,

3,4,5 -trimethylphenyl, 4-isopropylphenyl, 2-methyl-4,6-dinitrophenyl, 2-methyl-4-chlorophenyl, 2-chloro-4-t-butylphenyl, 2-chloro-4,S-dimethylphenyl, 2,fi-dimethyl-4-nitrosophenyl, 2,6-dimethyl-4-nitrophenyl, 2,4-dichloro-6-methylphenyl, 2,4-dichloro-S-methylphenyl, 2,6-di-t-butyl-4-nitrosophenyl, 2,6-dibromo-4-methylphenyl,

3 4-chloro-2,3,6-trimethylphenyl, 4-chloro-3-methylphenyl, 4-chloro-2-methylphenyl, 2-chloro-6-methylphenyl, 4-chloro-3,S-dimethylphenyl, 4-chloro-2,6-dimethylphenyl, 4-chloro-2,S-dimethylphenyl, 2-chloro-4,S-dimethylphenyl, 4-t-butyl-2-chlorophenyl, 2-bromo-4-methylphenyl, 4-bromo-3,S-dimethylphenyl, 2-bromo-4,S-dimethylphenyl, 2-methyl-3-nitrophenyl, 3-methyl-4-nitrophenyl, 4-methyl-3-nitrophenyl, 5-methyl-2-nitrophenyl, 2-methyl-4-nitrosophenyl, 3-methyl-4-nitrosopheny1 and 2-methoxy-4-rnethylphenyl and lower alkoxyphenyl,

such as 3,5-dimethoxyphenyl, 2,6-dimethoxyphenyl, 2,3-dimethoxyphenyl, 4-n-butoxyphenyl, 4-methoxyphenyl, 4-ethoxyphenyl, 2-ethoxy-4-nitrophenyl, 2-methoxy-4-nitrophenyl, 2-methoxy-4-chlorophenyl and 3-methoxyphenyl.

Examples of other phenyl groups are 4-nitrosophenyl, 2-chloro-4-nitrosophenyl, 2 chloromethyl-4-nitrophenyl, 3-trifiuoromethyl-2,4,6-trinitrophenyl, 4 cyanophenyl, 3- cyanophenyl, 2 cyanophenyl, 4-methylthiophenyl, 4-trifluoromethylphenyl, 3 trifluoromethylphenyl, 2,5 dichloro-4-methoxyphenyl, 2,6-dichloro 4 (methylsulfonyl)phenyl, 3,5-dichloro-4-(methylsulfonyl)phenyl and 2,5dichloro-4-methylthiophenyl.

Examples of other phenyl groups (R of the compounds of the present invention are 2-chloro-4-bromophenyl, 2,3 or 4-chlorophenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorophenyl, 2,3,4-, 2,3,6-, 2,3,5-, 2,4,5-, 2,4,6- or 3,4,5-trichlorophenyl, pentachlorophenyl, pentabromophenyl, pentafluorophenyl, 2,3,4,6-tetrachlorophenyl, 2,3, 5,6-tetrafiuorophenyl, 2,4,6-tribromophenyl, 2,4,6-triiodophenyl, 4-bromo-2,6-dichlorophenyl, 4-iodophenyl, 2-, 3- or 4-fiuorophenyl, 2-, 3- or 4bromophenyl and 4-iodophenyl.

In the description following, each of R to R X Y m, n, v, Z and Z is as defined above.

The compounds of formulas I, II and III are conveniently prepared from the precursors I, II and III;

by reaction with a carboxylic acid chloride or bromide or carboxylic acid anhydride in pyridine or by treatment with a carboxylic acid anhydride in the presence of sodium acetate. The reaction is generally conducted at about room temperature to reflux temperature for about one to forty-eight hours, shorter reaction time being favored by temperatures above room temperature. The precursors I, II and III are prepared by addition of water to the terminal olefinic bond using mercuric salt followed by 4 reduction according to application Ser. No. 59,762, filed July 30, 1970, now US. Pat. 3,709,914; application Ser. No. 60,636, filed Aug. 3, 1970, now abandoned; and application Ser. No. 100,787, filed Dec. 22, 1970, now abandoned, the disclosure of which is hereby incorporated by reference.

The term the residue of a carboxylic acid, as used herein, refers to the carboxylic acyl group of OR. The acyl group is determined by the particular carboxylic acid halide or carboxylic acid anhydride employed in the esterification of the hydroxyl precursors I, H and III. Although no upper limitation need be placed on the number of carbon atoms contained in the acyl group within the scope of the present invention, generally it contains from one to eighteen carbon atoms. Typical esters of the present invention include formate, acetate, propionate, enanthate, benzoate, trimethylacetate, trichloroacetate, trifiuoroacetate, t-butylacetate, phenoxyacetate, cyclo pentylpropionate, aminoacetate, fl-chloropropionate, adamantoate, octadec-9-enoate, dichloroacetate, butyrate, pentanoate, hexanoate, phenylacetate, p-methylbenzoate, B-phenylpropionate, 3,4-dimethylbenzoate, p-isopropylbenzoate, cyclohexylacetate, stearate, methacrylate, pchloromethylbenzoate, p-methoxybenzoate and p-nitrobenzoate.

The following examples are provided to illustrate the present invention. Temperature is given in degrees centigrade.

EXAMPLE 1 A mixture of 1 g. of 1-(7-hydroxy 3,7 dimethyloctanyloxy 4 ethylbenzene (7-hydroxy-3,7-dimethyloctyl p-ethylphenyl ether), 10 m1. of acetic anhydride and 0.5 g. of dry sodium acetate is refluxed for about five hours. After cooling, excess anhydride is removed by vacuum and the residue extracted with ether. The ethereal extract is washed, dried over magnesium sulfate and evaporated to yield the corresponding acetate [1-(7-acetoxy- 3,7'-dimethyloctanyloxy 4-ethylbenzene] The acetate of each of the hydroxyl compounds under Column I are prepared using the above procedure.

1- (7-hydroxy-3 ',7-dimethyloct-2-enyloxy) 4-ethylbenzene, 1-(7-hydroxy-3',7-dimethylnon-2'-enyloxy)-4ethylbenzene, 1-(5-hydroxy-l',5'-dimethylhexanyloxy)-4-ethylbenzene, 1-(7'-hydroxy-3',7'-dimethyloct- '-enyloxy)-3-chloro- 4-ethylbenzene, 1-(7-hydroxy-3,7-dimethy1oct-2-enyloxy)-3,4-

methylenedioxybenzene and methyl 4-(7-hydroxy-3',7'-dimethyloctanyloxy)phenyl ketone EXAMPLE 2 A mixture of 2 g. of dry 7-hydroxy-3,7-dimethyloctyl p-isopropylphenyl ether, 15 ml. of acetyl chloride and 20 ml. of dry pyridine under nitrogen is heated on a steam bath for about six hours. After cooling, the mixture is concentrated under vacuum and the residue taken up in ether. The ethereal extract is washed, dried over magnesium sulfate and evaporated to yield the corresponding acetate (7 acetoxy-3,7-dimethyloctyl p-isopropylphenyl ether).

The process of this example is repeated with the exception of using triethylamine in place of pyridine to yield 7-acetoxy-3,7-dimethyloctyl pis0pr0pylphenyl ether.

By use of the foregoing procedure, each of 7-hydroxy- 3,7-dimethy1octyl p-ethylphenyl ether and 7-hydroxy-3,7- dimethyloct-Z-enyl p-ethylphenyl ether is converted into the corresponding 7-chloroacetate, 7-dichloroacetate and 7-trichloroacetate using chloroacetyl chloride, dichloroacetyl chloride and trichloroacetyl chloride.

EXAMPLE 3 A mixture of ml. of dry formic acid and 2 g. of 3,7- dimethyloct-6-enyl p-ethylphenyl ether is heated at 50 for two hours and then poured onto ice cold potassium bicarbonate solution. The reaction is worked up by extraction with ether, washing the ethereal extract, drying over magnesium sulfate and evaporation to yield the formate of 7-hydroxy-3,7-dimethyloctyl p-ethylphenyl ether.

Using the above process, the iormates of formulas I, II and III are prepared from the corresponding precursor having an olefinic bond in the terminal group.

EXAMPLE 4 The process of Example 1 is repeated with the exception of using as the starting material, each of:

-7-hydroxy-3,7-diinethyloctyl 2,4,5-trichlorophenyl ether,

7-hydroxy-3,7-dimethyloctyl 2,3,4,6-tetrachlorophenyl ether,

7-hydroxy-3,7-dimethyloct-2-enyl 3-chloro-4-ethylpheny1 ether,

7-hydroxy-3,7-dimethylnon-2-eny1 3-chloro-4-ethylphenyl ether, and

7-hydroxy-3,7-dimethyloctyl 4-cyanophenyl ether to prepare the corresponding acetate esters.

The corresponding trifluoroacetate, propionate, n-butanoate, n-pentanoate and n-hexanoate esters of the above hydroxyl compounds are prepared according to the process of Example 1 using trifiuoroacetic anhydride, propionic anhydride, n-butyric anhydride, n-pentanoic anhydride and n-hexanoic anhydride or according to the process of Example 2 using the corresponding acid chloride.

What is claimed is:

1. A compound selected from those of the formulas I, II and III:

wherein, m is the positive integer one or two; n is the positive integer two or three; each of Z and Z' is hydrogen or taken together a carbon-carbon bond; each of R R R and R is lower alkyl; R is an acyl of a hydrocarbon carboxylic acid of one to eighteen carbon atoms or a halo-lower alkanoic acid; and R is the group in which X is halo, Y is lower alkyl, lower alkenyl, lower alkoxy, nitro, cyano, halornethyl, dihalomethyl, trihalomethy, lower alkylthio, lower alkylsulfinyl or lower alkylsulfonyl; p is zero or a positive integer of one to five; and q is zero or a positive integer of one to three, the sum of p and q being from one to five.

2. A compound according to claim 1 wherein each of R R R and R is methyl or ethyl.

3. A compound according to claim 2 wherein Y is lower alkyl.

4. A compound according to claim 3 wherein Y is lower alkyl of one to four carbon atoms; p is zero; q is one; m is one and n is two.

5. A compound of formula I or II according to claim 4 wherein Y is in the para position.

6. A compound according to claim 5 wherein R is an acyl group of one to six carbon atoms.

7. A compound according to claim 5 wherein R is an acyl group of two to six carbon atoms.

8. A compound according to claim 7 wherein each of R R and R is methyl.

9. A compound of formula I according to claim 8 wherein each of Z and Z is hydrogen.

10. A compound according to claim 3 wherein Y is lower alkyl of one to four carbon atoms; X is chloro or bromo; p is one to five; q is zero or one to three; m is one and n is two.

11. A compound of formula I or II according to claim 10 wherein Y is in the para position; X is in position three; p is one; q is One and R is an acyl group of one to six carbon atoms.

12. A compound according to claim 11 wherein R is an acyl group of two to six carbon atoms.

13. A compound according to claim 10 wherein X is in the para position; Y is in position three; p is one; q is one and R is an acyl group of one to six carbon atoms.

14. A compound according to claim 13 wherein R is an acyl group of two to six carbon atoms.

15. A compound according to claim 10 wherein q is zero and R is an acyl group of one to six carbon atoms.

16. A compound according to claim 15 wherein X is chloro.

17. A compound according to claim 16 wherein p is one to three.

18. A compound according to claim 15 wherein X is chloro and R is an acyl group of one to six carbon atoms.

19. A compound according to claim 18 wherein p is one to three.

20. The compound, 7-acetoxy-3,7-dimethyloct-2-enyl pethylphenyl ether, according to claim 1.

References Cited UNITED STATES PATENTS 3,385,899 5/1968 Weil et al. 260-488 CD 3,707,566 12/1972 Oreger et al. 260-488 CD VIVIAN GARNER, Primary Examiner US. Cl. X.R.

260-3405, 402, 404, 408, 410.5, 465 D, 465 F, 468 G, 468 R, 471 R, 473 G, 473 R, 476 R, 482 R, 486 R, 487, 592, 609 R, 612 D, 999 

